JP6778379B2 - Impact Resistant Reactive Hot Melt Adhesive Composition - Google Patents
Impact Resistant Reactive Hot Melt Adhesive Composition Download PDFInfo
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- JP6778379B2 JP6778379B2 JP2016118873A JP2016118873A JP6778379B2 JP 6778379 B2 JP6778379 B2 JP 6778379B2 JP 2016118873 A JP2016118873 A JP 2016118873A JP 2016118873 A JP2016118873 A JP 2016118873A JP 6778379 B2 JP6778379 B2 JP 6778379B2
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- Prior art keywords
- polyester polyol
- melt adhesive
- urethane prepolymer
- adhesive composition
- hot melt
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- 239000004831 Hot glue Substances 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 33
- 229920005906 polyester polyol Polymers 0.000 claims description 45
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000012790 adhesive layer Substances 0.000 claims description 18
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 11
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 235000007586 terpenes Nutrition 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 150000003505 terpenes Chemical class 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 229920001083 polybutene Polymers 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 230000001568 sexual effect Effects 0.000 claims 1
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- -1 aromatic diols Chemical class 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DHPWGEOXBYBHOY-YPKPFQOOSA-N (z)-2-dodecylbut-2-enedioic acid Chemical compound CCCCCCCCCCCC\C(C(O)=O)=C\C(O)=O DHPWGEOXBYBHOY-YPKPFQOOSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KMQONOBDGXYSII-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,1-diol Chemical compound CCC(C)CC(C)(C)C(O)O KMQONOBDGXYSII-UHFFFAOYSA-N 0.000 description 1
- ICCGPSONZQYELI-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,1-diol Chemical compound CCC(C)(C)CC(C)C(O)O ICCGPSONZQYELI-UHFFFAOYSA-N 0.000 description 1
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- INWVTRVMRQMCCM-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 INWVTRVMRQMCCM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CTZCDPNOAJATOH-UHFFFAOYSA-N cyclohexa-1,4-diene-1,2-dicarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)CC=CC1 CTZCDPNOAJATOH-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、反応性ホットメルト接着剤組成物に関するもので、特に耐衝撃性に優れる反応性ホットメルト接着剤組成物に関する。 The present invention relates to a reactive hot melt adhesive composition, and more particularly to a reactive hot melt adhesive composition having excellent impact resistance.
ホットメルト型接着剤は無溶剤型の接着剤であるため環境や人体への負荷が少なく、短時間接着が可能なので生産性向上に適した接着剤であり、製本、繊維、建材など産業界で広く利用されている。
ホットメルト型接着剤は、主成分が熱可塑性樹脂または反応性樹脂の2つに大別できる。主成分を熱可塑性樹脂としたホットメルト接着剤は、主にEVA(エチレン酢酸ビニル共重合体)が利用され、いわゆる、ホットメルト接着剤と呼ばれている。
一方、主成分を反応性樹脂としたホットメルト接着剤は、主にイソシアネート基末端のウレタンプレポリマーが利用され、反応性ホットメルト接着剤と呼ばれている。反応性ホットメルト接着剤は、接着後、接着剤自体の冷却固化により、短時間である程度の接着強度を発現する。その後、ウレタンプレポリマーの末端イソシアネート基が空気中や被着体表面の水分と反応することにより高分子量化、架橋を生じることにより接着剤層を形成して耐熱性が発現することにより、加熱時でも良好な接着強さ(接着強度)を示す。
Hot-melt adhesives are solvent-free adhesives that have less impact on the environment and the human body, and can be adhered in a short time, making them suitable for improving productivity. In the industrial world such as bookbinding, textiles, and building materials. Widely used.
Hot-melt adhesives can be broadly divided into two main components: thermoplastic resins and reactive resins. EVA (ethylene vinyl acetate copolymer) is mainly used as the hot melt adhesive whose main component is a thermoplastic resin, and it is a so-called hot melt adhesive.
On the other hand, the hot melt adhesive containing the main component as a reactive resin mainly uses a urethane prepolymer at the end of the isocyanate group, and is called a reactive hot melt adhesive. After bonding, the reactive hot melt adhesive develops a certain level of adhesive strength in a short time by cooling and solidifying the adhesive itself. After that, the terminal isocyanate group of the urethane prepolymer reacts with the moisture in the air or on the surface of the adherend to increase the molecular weight and crosslink the urethane prepolymer to form an adhesive layer and develop heat resistance during heating. However, it shows good adhesive strength (adhesive strength).
従来、携帯電話等のウェアラブル端末の表示部等のパーツ同士の接着には、両面テープが用いられることが多かった。ウェアラブル端末は、携帯して持ち歩くため、携帯時または利用時に誤って落としてしまうことがある。そのため、ウェアラブル端末の接着部分には、落下時の衝撃で貼り合せたパーツ同士が脱落しないように耐衝撃性が求められている(例えば、特許文献1)。
また、近年、ウェアラブル端末の小型化にともない、パーツ同士の接着部分面積が狭くなる傾向があり、また、複雑形状のパーツが増え、従来の両面テープによる接着方式では十分な接着力が得られなくなる課題を有していた。なお、テープによる接着幅が0.7mm以下になると、テープ加工が困難になると言われている。
Conventionally, double-sided tape has often been used to bond parts such as display parts of wearable terminals such as mobile phones. Since the wearable terminal is carried around, it may be accidentally dropped when it is carried or used. Therefore, the adhesive portion of the wearable terminal is required to have impact resistance so that the parts bonded together due to the impact at the time of dropping do not fall off (for example, Patent Document 1).
Further, in recent years, with the miniaturization of wearable terminals, the area of the adhesive portion between parts tends to become smaller, and the number of parts having complicated shapes increases, so that sufficient adhesive strength cannot be obtained by the conventional adhesive method using double-sided tape. I had a problem. It is said that tape processing becomes difficult when the adhesive width of the tape is 0.7 mm or less.
耐落下衝撃性を考慮した接着剤として、特許文献2および3が開示されている。ここで、特許文献2に開示されたホットメルト接着剤は有機溶剤を含有した接着剤であり、環境影響の観点で懸念がある。また、特許文献3に開示されたエポキシ接着剤は2液混合型の接着剤であり、取扱い上の課題がある。 Patent Documents 2 and 3 are disclosed as adhesives in consideration of drop impact resistance. Here, the hot melt adhesive disclosed in Patent Document 2 is an adhesive containing an organic solvent, and there is a concern from the viewpoint of environmental impact. Further, the epoxy adhesive disclosed in Patent Document 3 is a two-component mixed type adhesive, and has a problem in handling.
本発明は、極小部分でのパーツ同士の接着が可能な塗布性を有しながら、無溶剤タイプで、一液型であり、さらに耐衝撃性をも兼ね備えた反応性ホットメルト接着剤組成物を提供することにある。 The present invention provides a reactive hot-melt adhesive composition that is solvent-free, one-component, and has impact resistance, while having coating properties that allow parts to adhere to each other in extremely small areas. To provide.
前記課題を解決するため、本発明は、(1)ポリエステルポリオール(A)、ポリエーテルポリオール(B)とイソシアネート(C)を反応させて得られるイソシアネート基を有するウレタンプレポリマー(i)、及びウレタンプレポリマー(i)と非反応の成分(ii)を含有する反応性ホットメルト接着剤組成物であって、得られた接着剤層の機械的特性が、JIS K−7127で規定される引張弾性率が40MPa以下で、引張破壊応力が15MPa以上であり、かつ破断点伸度が1,000%以上の反応性ホットメルト接着剤組成物を提供するものである。
(2)ポリエステルポリオール(A)が結晶性ポリエステルポリオール(A−1)と非晶性ポリエステルポリオール(A−2)からなる(1)に記載の反応性ホットメルト接着剤組成物を提供するものである。
(3)非昌性ポリエステルポリオール(A−2)が分子量3,000以下のポリエステルポリオール(A−2−1)と分子量5,000以上のポリエステルポリオール(A−2−2)からなる(1)または(2)に記載の反応性ホットメルト接着剤組成物を提供するものである。
(4)ウレタンプレポリマー(i)と非反応の成分(ii)がポリブテン、ポリブタジエン、エステル系可塑剤、アクリル系可塑剤、ロジン系樹脂(ロジン樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂)、テルペン系(テルペン樹脂、水添テルペン樹脂)から選ばれるいずれか1種以上である(1)〜(3)のいずれかに記載の反応性ホットメルト接着剤組成物を提供するものである。
(5)ウレタンプレポリマー(i)と非反応の成分(ii)量が、ウレタンプレポリマー(i)100質量部に対して0.1〜10質量部である(1)〜(4)のいずれかに記載の反応性ホットメルト接着剤組成物を提供するものである。
In order to solve the above problems, the present invention comprises (1) a urethane prepolymer (i) having an isocyanate group obtained by reacting a polyester polyol (A), a polyether polyol (B) and an isocyanate (C), and a urethane. A reactive hot-melt adhesive composition containing a prepolymer (i) and a non-reactive component (ii), wherein the mechanical properties of the obtained adhesive layer are tensile elasticity defined by JIS K-7127. Provided is a reactive hot melt adhesive composition having a ratio of 40 MPa or less, a tensile fracture stress of 15 MPa or more, and a breaking point elongation of 1,000% or more.
(2) The reactive hot melt adhesive composition according to (1), wherein the polyester polyol (A) is composed of a crystalline polyester polyol (A-1) and an amorphous polyester polyol (A-2). is there.
(3) The non-changing polyester polyol (A-2) is composed of a polyester polyol (A-2-1) having a molecular weight of 3,000 or less and a polyester polyol (A-2-2) having a molecular weight of 5,000 or more (1). Alternatively, the reactive hot melt adhesive composition according to (2) is provided.
(4) The component (ii) that does not react with the urethane prepolymer (i) is polybutene, polybutadiene, ester plasticizer, acrylic plasticizer, rosin resin (rosin resin, rosin ester resin, hydrogenated rosin ester resin), The reactive hot melt adhesive composition according to any one of (1) to (3), which is one or more selected from terpene-based (terpene resin, hydrogenated terpene resin), is provided.
(5) Any of (1) to (4) in which the amount of the component (ii) that does not react with the urethane prepolymer (i) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer (i). It provides the reactive hot melt adhesive composition according to the above.
本発明により、極小部分でのパーツ同士の接着が可能な塗布性を有しながら、無溶剤タイプで、一液型であり、さらに耐衝撃性をも兼ね備えた反応性ホットメルト接着剤組成物を提供することにある。 According to the present invention, a reactive hot-melt adhesive composition which is a solvent-free type, a one-component type, and also has impact resistance while having a coatability capable of adhering parts to each other in a very small portion can be obtained. To provide.
本発明の反応性ホットメルト接着剤組成物(以下、接着剤組成物と略す場合もある。)は、ポリエステルポリオール(A)、ポリエーテルポリオール(B)とイソシアネート(C)を反応させて得られるイソシアネート基を有するウレタンプレポリマー(i)と非反応の成分(ii)とを含有する反応性ホットメルト接着剤組成物であって、この接着剤組成物から得られた接着剤層の機械的特性が、JIS K−7127で規定される引張弾性率が40MPa以下で、引張破壊応力が15MPa以上であり、かつ破断点伸度が1,000%以上であることを特徴としている。
本発明の反応性ホットメルト接着剤組成物から得られた接着剤層の機械的特性は、JIS K−7127で規定される引張弾性率が40MPa以下の接着剤層になっていることが特徴である。好ましい引張弾性率は2〜40MPaの範囲であり、特に好ましくは5〜30MPaの範囲である。引張弾性率が40MPa以下の接着剤層になっていることで、柔軟な接着剤層となり耐衝撃性が期待できる。
The reactive hot-melt adhesive composition of the present invention (hereinafter, may be abbreviated as an adhesive composition) is obtained by reacting a polyester polyol (A), a polyether polyol (B) and an isocyanate (C). A reactive hot-melt adhesive composition containing a urethane prepolymer (i) having an isocyanate group and a non-reactive component (ii), and the mechanical properties of the adhesive layer obtained from this adhesive composition. However, it is characterized in that the tensile reactivity defined by JIS K-7127 is 40 MPa or less, the tensile fracture stress is 15 MPa or more, and the break point elongation is 1,000% or more.
The mechanical properties of the adhesive layer obtained from the reactive hot-melt adhesive composition of the present invention are characterized by being an adhesive layer having a tensile elastic modulus of 40 MPa or less as defined by JIS K-7127. is there. The tensile elastic modulus is preferably in the range of 2 to 40 MPa, and particularly preferably in the range of 5 to 30 MPa. Since the adhesive layer has a tensile elastic modulus of 40 MPa or less, it becomes a flexible adhesive layer and can be expected to have impact resistance.
次に、本発明の反応性ホットメルト接着剤組成物から得られた接着剤層の機械的特性は、JIS K−7127で規定される引張破壊応力は15MPa以上である。上限値は100MPaであり、好ましい引張破壊応力は15〜50MPaの範囲であり、特に好ましくは15〜40MPaの範囲である。引張破壊応力が15MPa以上の接着剤層になっていることで、強靭な接着剤層となり、接着力向上が期待できる。 Next, the mechanical properties of the adhesive layer obtained from the reactive hot-melt adhesive composition of the present invention are that the tensile fracture stress defined by JIS K-7127 is 15 MPa or more. The upper limit is 100 MPa, and the preferable tensile fracture stress is in the range of 15 to 50 MPa, particularly preferably in the range of 15 to 40 MPa. Since the adhesive layer has a tensile fracture stress of 15 MPa or more, it becomes a tough adhesive layer, and improvement in adhesive strength can be expected.
さらに、本発明の反応性ホットメルト接着剤組成物から得られた接着剤層の機械的特性は、JIS K−7127で規定される破断点伸度は1,000%以上である。好ましい破断点伸度は1,000〜3,000%の範囲であり、特に好ましくは1,200〜2,000%の範囲である。破断点伸度が1,000%(10倍)以上の接着剤層になっていることで柔軟な接着剤層となり、耐衝撃性の向上が期待できる。 Further, the mechanical properties of the adhesive layer obtained from the reactive hot melt adhesive composition of the present invention are that the elongation at break point defined by JIS K-7127 is 1,000% or more. The break point elongation is preferably in the range of 1,000 to 3,000%, particularly preferably in the range of 1,200 to 2,000%. Since the adhesive layer has a breaking point elongation of 1,000% (10 times) or more, it becomes a flexible adhesive layer, and improvement in impact resistance can be expected.
本発明に用いるポリエステルポリオール(A)は、例えば、2〜15個の炭素原子および2つまたは3つのOH基を有する多価アルコールと、1種以上のポリカルボン酸、2〜14個の炭素原子(カルボキシル基中の炭素原子を含む)を有し、2〜6つのカルボキシル基を有するポリカルボン酸との重縮合反応によって生成される。本発明では、ジオールと一緒に直鎖ポリエステルジオールを生成するか、またはトリオールと一緒に分岐ポリエステルトリオールを生成する、ジカルボン酸が好ましい。逆に、分岐ポリエステルトリオールは、ジオールとトリカルボン酸との反応によって得ることもできる。ポリエステルポリオールのアルコール成分として、例えば、以下の化合物を使用することができる:エチレングリコール、1,2−プロパンジオール、1,3−プロパンジオール、異性体のブタンジオール、ペンタンジオール、ヘキサンジオール、2,2−ジメチル−1,3−プロパンジオール、2−メチルプロパンジオール、1,6−ヘキサンジオール、2,4,4−トリメチルヘキサンジオール、2,2,4−トリメチルヘキサンジオール、シクロヘキサンジオール、1,4−シクロヘキサンジメタノール、または芳香族ジオール、例えば、4,4´−ジヒドロキシジフェニルプロパン、ビスフェノールA、ビスフェノールF、ピロカテコール、レゾルシノール、ヒドロキノン。適当なカルボン酸は、例えば下記化合物である:フタル酸、イソフタル酸、テレフタル酸、マレイン酸、ドデシルマレイン酸、オクタデセニルマレイン酸、フマル酸、アコニット酸、1,2,4−ベンゼントリカルボン酸、1,2,3−プロパントリカルボン酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、セバシン酸、シクロヘキサン−1,2−ジカルボン酸、1,4−シクロヘキサンジエン−1,2−ジカルボン酸。なお、これら化合物のカルボン酸に代えて、その無水物を使用することもできる。 The polyester polyol (A) used in the present invention is, for example, a polyhydric alcohol having 2 to 15 carbon atoms and 2 or 3 OH groups, one or more polycarboxylic acids, and 2 to 14 carbon atoms. It is produced by a polycondensation reaction with a polycarboxylic acid having (containing a carbon atom in a carboxyl group) and having 2 to 6 carboxyl groups. In the present invention, a dicarboxylic acid is preferred, which produces a linear polyester diol with the diol or a branched polyester triol with the triol. Conversely, the branched polyester triol can also be obtained by reacting the diol with a tricarboxylic acid. As the alcohol component of the polyester polyol, for example, the following compounds can be used: ethylene glycol, 1,2-propanediol, 1,3-propanediol, isomeric butanediol, pentanediol, hexanediol, 2, 2-Diol-1,3-propanediol, 2-methylpropanediol, 1,6-hexanediol, 2,4,4-trimethylhexanediol, 2,2,4-trimethylhexanediol, cyclohexanediol, 1,4 -Cyclohexanedimethanol, or aromatic diols such as 4,4'-dihydroxydiphenylpropane, bisphenol A, bisphenol F, pyrocatechol, resorcinol, hydroquinone. Suitable carboxylic acids are, for example, the following compounds: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, dodecylmaleic acid, octadecenylmaleic acid, fumaric acid, adipic acid, 1,2,4-benzenetricarboxylic acid. , 1,2,3-Propanetricarboxylic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, cyclohexane-1,2-dicarboxylic acid, 1,4-cyclohexanediene-1,2-dicarboxylic acid acid. In addition, instead of the carboxylic acid of these compounds, the anhydride can also be used.
ポリエステルポリオール(A)は、結晶性ポリエステルポリオール(A−1)と非晶性ポリエステルポリオール(A−2)からなり、結晶性及び非晶性の区別は25℃での状態で判断する。すなわち、本発明のポリエステルポリオール(A)は、25℃で結晶状態であるポリエステルポリオールを結晶性ポリエステルポリオール(A−1)とし、25℃で非結晶状態であるポリエステルポリオールを非晶性ポリエステルポリオール(A−2)とする。 The polyester polyol (A) is composed of a crystalline polyester polyol (A-1) and an amorphous polyester polyol (A-2), and the distinction between crystalline and amorphous is judged at 25 ° C. That is, in the polyester polyol (A) of the present invention, a polyester polyol in a crystalline state at 25 ° C. is a crystalline polyester polyol (A-1), and a polyester polyol in a non-crystalline state at 25 ° C. is an amorphous polyester polyol (a non-crystalline polyester polyol). A-2).
加えて、前記結晶性ポリエステルポリオール(A−1)の数平均分子量としては、防水性や接着性の観点から、500〜10,000の範囲が好ましく、好ましくは1,000〜8,000の範囲である。なお、結晶性ポリエステルポリオール(A−1)の数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)によるポリスチレン換算により決定される値である。GPCの測定には、テトラヒドロフランを溶離液として、流量1.0ml/minで、日立化成製HPLC用充填カラム「Gelpack GLA130−S」、「Gelpack GLA150−S」および「Gelpack GLA160−S」を連結使用して、カラム温度40℃、検出器にRIを用いて測定する。 In addition, the number average molecular weight of the crystalline polyester polyol (A-1) is preferably in the range of 500 to 10,000, preferably in the range of 1,000 to 8,000, from the viewpoint of waterproofness and adhesiveness. Is. The number average molecular weight of the crystalline polyester polyol (A-1) is a value determined by polystyrene conversion by gel permeation chromatography (GPC). For GPC measurement, Hitachi Chemical's HPLC packing columns "Gelpack GLA130-S", "Gelpack GLA150-S" and "Gelpack GLA160-S" are connected and used at a flow rate of 1.0 ml / min using tetrahydrofuran as an eluent. Then, the column temperature is 40 ° C., and the detector is measured using RI.
非晶性ポリエステルポリオール(A−2)は、分子量3,000以下のポリエステルポリオール(A−2−1)と分子量5,000以上のポリエステルポリオール(A−2−2)からなる。
分子量の小さい非晶性ポリエステルポリオール(A−2−1)の数平均分子量は3,000以下である。下限値は500であり、初期接着性を向上できる観点で決定した。なお、分子量の小さい非晶性ポリエステルポリオール(A−2−1)の数平均分子量としては500〜3,000の範囲が好ましく、1,000〜3,000の範囲が特に好ましい。
The amorphous polyester polyol (A-2) is composed of a polyester polyol (A-2-1) having a molecular weight of 3,000 or less and a polyester polyol (A-2-2) having a molecular weight of 5,000 or more.
The number average molecular weight of the amorphous polyester polyol (A-2-1) having a small molecular weight is 3,000 or less. The lower limit is 500, which is determined from the viewpoint of improving the initial adhesiveness. The number average molecular weight of the amorphous polyester polyol (A-2-1) having a small molecular weight is preferably in the range of 500 to 3,000, and particularly preferably in the range of 1,000 to 3,000.
また、非晶性ポリエステルポリオール(A−2)で分子量の大きい非晶性ポリエステルポリオール(A−2−2)の数平均分子量は5,000以上である。上限値は20,000であり、防水性や柔軟性、耐衝撃性、塗布性等を向上できる観点で決定した。なお、分子量の大きい非晶性ポリエステルポリオール(A−2−2)の数平均分子量としては5,000〜12,000の範囲が好ましく、5,000〜10,000の範囲が特に好ましい。なお、前記非晶性ポリエステルポリオール(A−2−1)及び非晶性ポリエステルポリオール(A−2−2)の数平均分子量は、前記した結晶性ポリエステルポリオール(A−1)の数平均分子量と同様にGPC(ゲルパーミエーションクロマトグラフィー)測定して得られた値である。 Further, the amorphous polyester polyol (A-2) having a large molecular weight has a number average molecular weight of 5,000 or more. The upper limit is 20,000, which was determined from the viewpoint of improving waterproofness, flexibility, impact resistance, coatability, and the like. The number average molecular weight of the amorphous polyester polyol (A-2-2) having a large molecular weight is preferably in the range of 5,000 to 12,000, and particularly preferably in the range of 5,000 to 10,000. The number average molecular weight of the amorphous polyester polyol (A-2-1) and the amorphous polyester polyol (A-2-2) is the same as the number average molecular weight of the crystalline polyester polyol (A-1). Similarly, it is a value obtained by GPC (gel permeation chromatography) measurement.
ポリエーテルポリオール(B)は、塗布後の適度な溶融粘度やオープンタイム(貼り合わせ可能時間)を調整して優れた作業性や接着性、防水性及び柔軟性等を付与するものであり、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、ポリテトラメチレングリコール、エチレンオキサイド変性ポリプロピレングリコール等を用いることができる。
ポリエーテルポリオール(B)の数平均分子量は、接着性や柔軟性の観点から、500〜6,000の範囲が好ましく、1,000〜5,000の範囲がより好ましい。なお、ポリエーテルポリオール(B)の数平均分子量は、前記した結晶性ポリエステルポリオール(A−1)の数平均分子量と同様の方法(GPC)で測定して得られた値である。
The polyether polyol (B) imparts excellent workability, adhesiveness, waterproofness, flexibility, etc. by adjusting an appropriate melt viscosity and open time (bonding time) after coating, for example. , Polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, ethylene oxide-modified polypropylene glycol and the like can be used.
The number average molecular weight of the polyether polyol (B) is preferably in the range of 500 to 6,000, more preferably in the range of 1,000 to 5,000, from the viewpoint of adhesiveness and flexibility. The number average molecular weight of the polyether polyol (B) is a value obtained by measuring by the same method (GPC) as the number average molecular weight of the crystalline polyester polyol (A-1) described above.
本発明のイソシアネート化合物(C)としては、ジイソシアネートを用いることが好ましく、例えば、ジフェニルメタンジイソシアネート、ジメチルジフェニルメタンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、p−フェニレンジイソシアネート、イソフォロンジイソシアネート等を用いることができる。 As the isocyanate compound (C) of the present invention, it is preferable to use diisocyanate, for example, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, p-phenylenediisocyanate, isophorone. Diisocyanate or the like can be used.
従って、本発明の反応性ホットメルト接着剤組成物中において、ポリイソシアネート化合物とポリオールとを混合し、ウレタンプレポリマー(i)としてもよく、また、予めポリイソシアネート化合物とポリオールからウレタンプレポリマー(i)を合成し、これを本発明の接着剤組成物に添加してもよい。
イソシアネート基を有するウレタンプレポリマー(i)を合成する場合の、本発明におけるポリイソシアネート化合物とポリオールとの混合割合は、ポリイソシアネート化合物のイソシアネート基(NCO)当量/ポリオールの水酸基(OH)当量が1.6〜3.0であり、好ましくは1.8〜2.5の範囲である。NCO/OH比が1.6未満では、得られるプレポリマー(i)の粘度が高くなり塗布作業性の低下を招く。一方、NCO/OH比が3.0を超えると湿気硬化反応の際に発泡を生じやすくなり、接着性を低下させるおそれがある。
Therefore, in the reactive hot melt adhesive composition of the present invention, the polyisocyanate compound and the polyol may be mixed to form a urethane prepolymer (i), or the polyisocyanate compound and the polyol may be mixed with a urethane prepolymer (i) in advance. ) May be synthesized and added to the adhesive composition of the present invention.
When synthesizing the urethane prepolymer (i) having an isocyanate group, the mixing ratio of the polyisocyanate compound and the polyol in the present invention is such that the isocyanate group (NCO) equivalent of the polyisocyanate compound / the hydroxyl group (OH) equivalent of the polyol is 1. It is .6 to 3.0, preferably in the range of 1.8 to 2.5. If the NCO / OH ratio is less than 1.6, the viscosity of the obtained prepolymer (i) becomes high and the coating workability is deteriorated. On the other hand, if the NCO / OH ratio exceeds 3.0, foaming is likely to occur during the moisture curing reaction, which may reduce the adhesiveness.
本発明のウレタンプレポリマー(i)と非反応の成分(ii)は、ポリブテン、ポリブタジエン、エステル系可塑剤、アクリル系可塑剤、ロジン系樹脂(ロジン樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂)、テルペン系(テルペン樹脂、水添テルペン樹脂)から選ばれるいずれか1種以上である。
ウレタンプレポリマー(i)と非反応の成分(ii)は水酸基などの活性水素を有しておらず、ウレタンプレポリマー(i)と反応しないことが求められ、配合量としては、湿気硬化性、接着性等の観点から、反応性ホットメルト接着剤の0.1部〜10質量部の範囲が好ましく、0.2〜5質量部の範囲がより好ましい。
ウレタンプレポリマー(i)と非反応の成分(ii)は主成分であるウレタンプレポリマーに取り込まれないことから、接着剤から得られた接着剤層に衝撃が加わった際に緩和する効果が得られる。
The component (ii) that does not react with the urethane prepolymer (i) of the present invention is polybutene, polybutadiene, ester plasticizer, acrylic plasticizer, rosin resin (rosin resin, rosin ester resin, hydrogenated rosin ester resin). , One or more selected from terpen type (terpene resin, hydrogenated terpene resin).
The urethane prepolymer (i) and the non-reactive component (ii) do not have active hydrogen such as a hydroxyl group and are required not to react with the urethane prepolymer (i). From the viewpoint of adhesiveness and the like, the range of 0.1 to 10 parts by mass of the reactive hot melt adhesive is preferable, and the range of 0.2 to 5 parts by mass is more preferable.
Since the urethane prepolymer (i) and the non-reactive component (ii) are not incorporated into the urethane prepolymer which is the main component, the effect of alleviating the impact when the adhesive layer obtained from the adhesive is applied is obtained. Be done.
本発明のウレタンプレポリマー(i)と非反応の成分(ii)量が、ウレタンプレポリマー(i)100質量部に対して0.1〜10質量部である反応性ホットメルト接着剤組成物である。非反応の成分(ii)量が、ウレタンプレポリマー(i)100質量部に対して0.1質量部以上で耐衝撃性に優れた反応性ホットメルト接着剤組成物が得られる。一方、非反応の成分(ii)量が、ウレタンプレポリマー(i)100質量部に対して10質量部以下であれば良好な接着力を示す。 In a reactive hot melt adhesive composition in which the amount of the component (ii) that does not react with the urethane prepolymer (i) of the present invention is 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer (i). is there. A reactive hot-melt adhesive composition having excellent impact resistance can be obtained when the amount of the non-reactive component (ii) is 0.1 part by mass or more with respect to 100 parts by mass of the urethane prepolymer (i). On the other hand, if the amount of the non-reactive component (ii) is 10 parts by mass or less with respect to 100 parts by mass of the urethane prepolymer (i), good adhesive strength is exhibited.
更に前記反応性ホットメルト接着剤組成物には触媒(ジブチルチンジラウレート、ジブチルチオンオクテート、ジメチルシクロヘキシルアミン、ジメチルベンジルアミン、トリオクチルアミン等)、顔料、酸化防止剤、紫外線吸収剤、界面活性剤、難燃剤、充填剤等を適量配合しても良い。 Further, the reactive hot melt adhesive composition includes a catalyst (dibutyltin dilaurate, dibutylthione octate, dimethylcyclohexylamine, dimethylbenzylamine, trioctylamine, etc.), a pigment, an antioxidant, an ultraviolet absorber, and a surfactant. , Flame retardant, filler, etc. may be blended in an appropriate amount.
以下、本発明を実施例で説明するが、本発明はこれらの実施例に限定されるものではない。なお、特にことわりのない限り、部は質量部である。 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, parts are parts by mass.
(実施例1〜10、比較例1〜4)
予め真空乾燥機により脱水処理したアジピン酸と1,6ヘキサンジオールを主成分とするポリエステルポリオール(水酸基数:2、数平均分子量5,000)20部と、アジピン酸とエチレングリコールを主成分とするポリエステルポリオール(水酸基数:2、数平均分子量2,000)25部と、イソフタル酸とネオペンチルグリコールを主成分とするポリエステルポリオール(水酸基数:2、数平均分子量2,000)25部と、アゼライン酸とエチレングリコールを主成分とするポリエステルポリオール(水酸基数:2、数平均分子量8,000)5部と、ポリプロピレングリコール(水酸基数:2、数平均分子量2,000、旭硝子株式会社製:EXENOL2020)25部と、ジフェニルメタンジイソシアネート(イソシアネート基数:2、日本ポリウレタン工業株式会社製:ミリオネートMT)20部とポリブテン(日油株式会社製:HV−30SH)0.5部を混合し、所定量加え均一に混合した後、110℃で2時間反応させ、更に110℃で2時間減圧脱泡攪拌し、イソシアネート基を有するウレタンプレポリマー(i)と非反応成分(ii)を含む、反応性ホットメルト接着剤組成物を得た。調整した各接着剤の配合を表1に示す。
(Examples 1 to 10, Comparative Examples 1 to 4)
20 parts of polyester polyol (number of hydroxyl groups: 2, number average molecular weight 5,000) containing adipic acid and 1,6 hexanediol as main components, which have been dehydrated in advance by a vacuum dryer, and adipic acid and ethylene glycol as main components. 25 parts of polyester polyol (number of hydroxyl groups: 2, number average molecular weight 2,000), 25 parts of polyester polyol (number of hydroxyl groups: 2, number average molecular weight 2,000) containing isocyanate and neopentyl glycol as main components, and azeline 5 parts of polyester polyol (number of hydroxyl groups: 2, number average molecular weight 8,000) containing acid and ethylene glycol as main components, and polypropylene glycol (number of hydroxyl groups: 2, number average molecular weight 2,000, manufactured by Asahi Glass Co., Ltd .: EXENOL2020) Mix 25 parts, 20 parts of diphenylmethane diisocyanate (number of isocyanate groups: 2, manufactured by Nippon Polyester Industry Co., Ltd .: Millionate MT) and 0.5 part of polybutene (manufactured by Nikko Co., Ltd .: HV-30SH), and add a predetermined amount uniformly. After mixing, the reaction is carried out at 110 ° C. for 2 hours, further defoamed and stirred at 110 ° C. for 2 hours under reduced pressure, and the reactive hot melt adhesive containing the urethane prepolymer (i) having an isocyanate group and the non-reactive component (ii) is contained. The composition was obtained. Table 1 shows the composition of each adjusted adhesive.
作製した反応性ホットメルト接着剤組成物(実施例1〜10、比較例1〜4)の試験結果、評価方法を以下に説明する。 The test results and evaluation methods of the produced reactive hot melt adhesive composition (Examples 1 to 10 and Comparative Examples 1 to 4) will be described below.
<粘度(溶融粘度)>
BH−HH型少量回転粘度計(東機産業株式会社製)を用いて下記条件にて測定した。
ロータ:4号ロータ
試料量:15g
回転数:50rpm
温度:120℃
<Viscosity (melt viscosity)>
The measurement was performed under the following conditions using a BH-HH type small amount rotational viscometer (manufactured by Toki Sangyo Co., Ltd.).
Rotor: No. 4 rotor Sample amount: 15 g
Rotation speed: 50 rpm
Temperature: 120 ° C
<機械的特性>
作製した反応性ホットメルト接着剤組成物試料を100℃に溶融し、縦15mm×横40mm×厚さ100μmの接着剤層の皮膜を作成し、25℃、50%RHの恒温槽に7日間放置し接着剤層の機械的特性(引張弾性率(MPa)、引張破壊応力(MPa)、破断点伸度(%))をJIS K−7127に準拠して引張試験機(株式会社島津製作所製オートグラフAGS−X)を用いて測定した。
<Mechanical characteristics>
The prepared reactive hot-melt adhesive composition sample was melted at 100 ° C. to prepare a film of an adhesive layer of length 15 mm × width 40 mm × thickness 100 μm, and left in a constant temperature bath at 25 ° C. and 50% RH for 7 days. The mechanical properties (tensile elastic modulus (MPa), tensile fracture stress (MPa), breaking point elongation (%)) of the adhesive layer are set according to JIS K-7127, which is a tensile tester (Auto manufactured by Shimadzu Corporation). It was measured using the graph AGS-X).
<接着力>
作製した反応性ホットメルト接着剤組成物試料を100℃に溶融し、温度25℃、50%RH(相対湿度)の環境下で、ポリカーボネート製の板上に、縦15mm×横40mm×厚さ100μmの接着剤層の皮膜を作成後、縦250mm×横25mm×厚さ100μmのポリカーボネート製フィルムと圧着し、25℃、50%RH(相対湿度)の恒温槽に7日間放置し、90°ピール試験(ピール速度:100mm/分)を行い、接着強度を測定した。
<Adhesive strength>
The prepared reactive hot-melt adhesive composition sample was melted at 100 ° C. and placed on a polycarbonate plate at a temperature of 25 ° C. and 50% RH (relative humidity) on a polycarbonate plate (length 15 mm × width 40 mm × thickness 100 μm). After forming a film of the adhesive layer of, it is pressure-bonded to a polycarbonate film of length 250 mm × width 25 mm × thickness 100 μm, and left in a constant temperature bath at 25 ° C. and 50% RH (relative humidity) for 7 days to perform a 90 ° peel test. (Peel speed: 100 mm / min) was performed, and the adhesive strength was measured.
<耐衝撃性>
作製した反応性ホットメルト接着剤組成物試料を100℃に溶融し、内径0.25mmの精密ノズル(武蔵エンジニアリング株式会社製SHN−0.25N)を取り付けたシリンンジ容器(武蔵エンジニアリング株式会社製PSY−30E)に入れて、予め100℃に加熱されたディスペンサー(武蔵エンジニアリング株式会社製SHOTMASTER 200DS」を用いて吐出させ、被着体A(ポリカーボネート製板:幅100mm×長さ50mm、中心部に内径20mmの穴)上に40mm×40mmの正方形を描くように塗布して、被着体B(アクリル製板:幅50mm×長さ50mm)を貼り合わせ、接着剤の幅0.5mm、厚みが0.1mmになるように調整し積層体を作製した。23℃、50%RH(相対湿度)の環境下で3日間放置して作製した積層体を23℃、50%RH(相対湿度)の環境下で、被着体B側を下向きとして、前記積層体の被着体A側をデュポン衝撃機に固定した。次いで、撃ち型(半径6.25mm)を、前記積層体の被着体Aの穴から被着体Bの接着剤を塗布した側の表面に上方から接触させるようにして配置した。
その後、上方200mm、250mm、300mmの高さから荷重300gの錘を落下させ、前記撃ち型に衝突させることにより、前記積層体の前記被着体Bに鉛直方向下方に力を加え、被着体Bの剥がれの有無を確認した。結果、剥がれが無かったものは「○」、剥がれたものは「×」と評価した。
<Impact resistance>
The prepared reactive hot melt adhesive composition sample was melted at 100 ° C., and a silica container (PSY-manufactured by Musashi Engineering Co., Ltd.) equipped with a precision nozzle (SHN-0.25N manufactured by Musashi Engineering Co., Ltd.) having an inner diameter of 0.25 mm was attached. 30E) and discharged using a dispenser (SHOTMASTER 200DS manufactured by Musashi Engineering Co., Ltd.) preheated to 100 ° C., and adherend A (polycarbonate plate: width 100 mm x length 50 mm, inner diameter 20 mm at the center). A 40 mm x 40 mm square is applied on the hole), and the adherend B (acrylic plate: width 50 mm x length 50 mm) is adhered to the adhesive to have a width of 0.5 mm and a thickness of 0. The laminate was adjusted to 1 mm to prepare a laminate. The laminate was left to stand for 3 days in an environment of 23 ° C. and 50% RH (relative humidity), and the laminate was prepared in an environment of 23 ° C. and 50% RH (relative humidity). Then, the adherend A side of the laminated body was fixed to the Dupont impact machine with the adherend B side facing downward. Next, a shooting type (radius 6.25 mm) was formed in the hole of the adherend A of the laminated body. It was arranged so as to be in contact with the surface of the adherend B on the side to which the adhesive was applied from above.
After that, a weight having a load of 300 g is dropped from heights of 200 mm, 250 mm, and 300 mm above and collides with the shooting mold to apply a force downward in the vertical direction to the adherend B of the laminate to apply the adherend. It was confirmed whether or not B was peeled off. As a result, those that did not peel off were evaluated as "○", and those that did peel off were evaluated as "x".
本発明の反応性ホットメルト接着剤組成物である実施例1〜10の各試料は耐衝撃性に優れることが分かる。
一方、比較例1及び2は、非反応成分(ii)とポリエステルポリオール(A−2−2)を含有しないため伸度が低くなり、耐衝撃性が不良であった。
また、比較例3は、ポリエステルポリオール(A−1)を含有しないため、引張破壊応力が低く、耐衝撃性が不良であった。
比較例4は、ポリエーテルポリオール(B)を含有しないため、引張弾性率が高いものの、伸度が低く、耐衝撃性が不良であった。
比較例5は、非反応成分(ii)を20部含有した態様であるが、接着性および耐衝撃性が不良であった。
It can be seen that each sample of Examples 1 to 10 which is the reactive hot melt adhesive composition of the present invention has excellent impact resistance.
On the other hand, Comparative Examples 1 and 2 did not contain the non-reactive component (ii) and the polyester polyol (A-2-2), so that the elongation was low and the impact resistance was poor.
Further, in Comparative Example 3, since the polyester polyol (A-1) was not contained, the tensile fracture stress was low and the impact resistance was poor.
In Comparative Example 4, since the polyether polyol (B) was not contained, the tensile elastic modulus was high, but the elongation was low and the impact resistance was poor.
Comparative Example 5 was an embodiment containing 20 parts of the non-reactive component (ii), but had poor adhesiveness and impact resistance.
Claims (1)
ポリエステルポリオール(A)が、結晶性ポリエステルポリオール(A−1)と非晶性ポリエステルポリオール(A−2)からなり、
非晶性ポリエステルポリオール(A−2)が、分子量3,000以下のポリエステルポリオール(A−2−1)と分子量5,000以上のポリエステルポリオール(A−2−2)からなり、
ウレタンプレポリマー(i)と非反応の成分(ii)が、ポリブテン、ポリブタジエン、エステル系可塑剤、ロジン樹脂、ロジンエステル樹脂、水添ロジンエステル樹脂、テルペン樹脂及び水添テルペン系樹脂から選ばれるいずれか1種以上であり、
ウレタンプレポリマー(i)と非反応の成分(ii)量が、ウレタンプレポリマー(i)100質量部に対して0.1〜10質量部であり、
得られた接着剤層の機械的特性が、JIS K−7127で規定される引張弾性率が40MPa以下で、引張破壊応力が15MPa以上であり、かつ破断点伸度が1,000%以上の反応性ホットメルト接着剤組成物。 A urethane prepolymer (i) having an isocyanate group obtained by reacting a polyester polyol (A), a polyether polyol (B) and an isocyanate (C), and a component (ii) that does not react with the urethane prepolymer (i). Reactive hot melt adhesive composition contained
The polyester polyol (A) is composed of a crystalline polyester polyol (A-1) and an amorphous polyester polyol (A-2).
The amorphous polyester polyol (A-2) is composed of a polyester polyol (A-2-1) having a molecular weight of 3,000 or less and a polyester polyol (A-2-2) having a molecular weight of 5,000 or more.
The urethane prepolymer (i) and the non-reactive component (ii) are selected from polybutene, polybutadiene, ester plasticizer, rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin and hydrogenated terpene resin. Or more than one
The amount of the component (ii) that does not react with the urethane prepolymer (i) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the urethane prepolymer (i).
The mechanical properties of the obtained adhesive layer are a reaction in which the tensile elastic modulus specified by JIS K-7127 is 40 MPa or less, the tensile fracture stress is 15 MPa or more, and the elongation at break is 1,000% or more. Sexual hot melt adhesive composition.
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